Materials Including Thermally Reversible Gels

ABSTRACT

Materials are disclosed that include or are based on thermally reversible gels, such as thermally reversible gelled fluids, oil gels and solvent gel resins. In an exemplary embodiment, a material includes at least one filler in a thermally reversible gel.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.15/714,425 filed Sep. 25, 2017, which published as US2018/0079946 onMar. 22, 2018 and which issues as U.S. Pat. No. 10,087,351 on Oct. 2,2018.

U.S. patent application Ser. No. 15/714,425 is a continuation-in-part ofU.S. patent application Ser. No. 15/043,808 filed Feb. 15, 2016, whichpublished as US2016/0160104 on Jun. 9, 2016 and issued as U.S. Pat. No.9,771,508 on September 26, 2017.

U.S. Patent Application No. 15/043,808 is a continuation-in-part of U.S.Patent Application No. 12/710,538 filed February 23, 2010, whichpublished as US2011/0204280 on August 25, 2011 and issued as U.S. Pat.No. 9,260,645 on Feb. 16, 2016.

The entire disclosures of the above applications are incorporated hereinby reference in its entirety.

FIELD

The present disclosure relates generally to materials including or basedon thermally reversible gels, such as thermally reversible gelled fluid,oil gel and solvent gel resins.

BACKGROUND

This section provides background information related to the presentdisclosure which is not necessarily prior art.

Electrical components, such as semiconductors, integrated circuitpackages, transistors, etc., typically have pre-designed temperatures atwhich the electrical components optimally operate. Ideally, thepre-designed temperatures approximate the temperature of the surroundingair. But the operation of electrical components generates heat. If theheat is not removed, the electrical components may then operate attemperatures significantly higher than their normal or desirableoperating temperature. Such excessive temperatures may adversely affectthe operating characteristics of the electrical components and theoperation of the associated device.

To avoid or at least reduce the adverse operating characteristics fromthe heat generation, the heat should be removed, for example, byconducting the heat from the operating electrical component to a heatsink. The heat sink may then be cooled by conventional convection and/orradiation techniques. During conduction, the heat may pass from theoperating electrical component to the heat sink either by direct surfacecontact between the electrical component and heat sink and/or by contactof the electrical component and heat sink surfaces through anintermediate medium or thermal interface material. The thermal interfacematerial may be used to fill the gap between thermal transfer surfaces,in order to increase thermal transfer efficiency as compared to havingthe gap filled with air, which is a relatively poor thermal conductor.Most especially in the cases of phase changes and thermal greases, asignificant gap is not required and the purpose of the thermal interfacematerial may be just to fill in the surface irregularities betweencontacting surfaces. In some devices, an electrical insulator may alsobe placed between the electronic component and the heat sink, in manycases this is the thermal interface material itself.

DETAILED DESCRIPTION

Example embodiments will now be described more fully.

Many thermal interface materials are based on silicone resin systems.But in some applications, a silicone-free thermal interface compliantgap filler is desired, such as for fiber optic applications, automotivemodules, disk drives, plasma display panels, liquid crystal displaypanels, etc. Ideally, silicone free thermal interface materials wouldnot only be silicone free, but they would also be extremely soft,elastomeric, of reasonable cost, temperature and atmospherically stable,and free of significant resin migration. But silicone freethermally-conductive gap fillers are often based on acrylic,polyurethane, polyolefin, etc. resin systems, which suffer from the factthat they produce a relatively hard elastomer, resulting in anon-compliant gap filler. After recognizing the above, the inventorhereof has developed and now discloses various exemplary embodiments ofsilicone-free, compliant thermal interface materials that include or arebased on thermally reversible gels, such as thermally reversible gelledfluids, oil gels and solvent gel resins. In addition, the inventorhereof has also developed and discloses herein other exemplaryembodiments of thermal interface materials that include or are based onthermally reversible gels, some of which may be silicone-based gels.Accordingly, while some exemplary embodiments disclosed herein areentirely or substantially free of silicone, other exemplary embodimentsmay include silicone. In the embodiments that are substantially free ofsilicone, a thermal interface material may include a de minimis ortrivial amount of silicone, where that amount of silicone is low enoughso as to not adversely affect the end use applications of the thermalinterface material, which might otherwise be adversely affected by thepresence of a more than trivial amount of silicone. Some embodiments ofa thermal interface material are based on an oil gel resin system andare silicone free (e.g., entirely silicone free, substantially siliconefree), extremely soft, elastomeric, of reasonable cost, temperature andatmospherically stable and free of significant resin migration.

By way of background, the term “gel” as used herein may generally referto semi-rigid colloidal dispersion of a solid with a liquid or gas, asjelly, glue, etc. A “gel” may generally be a solid, jelly-like materialthat can have properties ranging from soft and weak to hard and tough.“Gel” as used herein may be defined as a substantially dilute elastic ormicelle network that exhibits no flow when in the steady-state. Byweight, a gel may be mostly liquid, yet they behave like solids due to athree-dimensional network within the liquid. It is the network withinthe liquid that gives gel its structure (hardness). With a gel, a solidthree-dimensional network generally spans the volume of a liquid medium.By way of further background, “a thermally reversible gel” as usedherein refers to a gel that may be heated to a liquid and cooled to agel over and over again, such that the thermally reversible gel may thusbe reused, reformed, recycled, etc. by reheating the gel to a liquid andcooling back to a gel. In some cases, this transition temperature atwhich the thermally reversible gel changes from substantially liquid toa gel may be below room temperature.

As recognized by the inventor hereof, thermally reversible gels, such asthermally reversible gelled fluids, oil gels and solvent gel resins, arewell suited for use as a base for thermal interface materials.Accordingly, the inventor has disclosed herein example embodiments ofnovel thermal interface materials and methods of making such novelthermal interface materials that include or are based on thermallyreversible gels, such as thermally reversible gelled fluids, oil gelsand solvent gel resins. The thermal interface materials may also includeat least one thermally conductive filler in the thermally reversiblegel.

Also, the inventor has recognized that thermally reversible gels, suchas oil gels, may be specifically formulated to soften at a giventemperature. This, in turn, may allow for greater customization for someof the inventor's exemplary embodiments of thermal interface materialsthat are based on oil gel resin systems as compared to some thermalinterface materials based on a silicone resin system. For example, someof the inventor's exemplary embodiments provide thermal interfacematerials based on oil gel resin systems in which the oil gel has beenselected or formulated such that the thermal interface material beginsto soften at a temperature of about 150 degrees Celsius. In otherembodiments, a thermal interface material may include an oil gel resinsystem in which the oil gel is formulated to soften at a temperaturehigher or less than 150 degrees Celsius, such as within a temperaturefrom about 5 degrees Celsius to about 200 degrees Celsius.

In various exemplary embodiments, thermally conductive filler is addedto oil (or other gellible fluid) and gelling agent to produce athermally conductive grease, phase change, putty, and/or gap filler. Byusing an oil gel (or other suitable thermally reversible gel) as thebase for a thermal interface material, the inventor hereof hasdiscovered that it is possible to produce a gap filler with physicalproperties comparable to that of traditional silicone based gap filleryet with no occurrence of silicone migration or volatility due to theabsence of silicone in the formulation.

A thermally reversible gel is generally a blend of one or more oilsand/or solvents and one or more gelling agents. The majority of theblend typically comprises the oil(s) and/or solvent(s). Suitable oils orother materials for a thermally reversible gel that may be used inexemplary embodiments of the present disclosure include naphthenic oils,paraffinic oils, iso-paraffinic oils, hydrocarbon oils, aromatic oils,paraffinic solvents, isoparaffinic solvents (e.g., Isopar), naphthenicsolvents, silicone oils, etc., mineral oils, natural oils (such assoybean oils, coconut oils and ester oils) and synthetic products (suchas polybutene or polyisobutene). Suitable gelling agents that may beused in exemplary embodiments of the present disclosure include waxes,fumed silica, fatty acid soaps, thermoplastic materials (e.g.,thermoplastic elastomers, etc.) and polymers (e.g., block copolymers,etc.). Oil gels are commonly used for air fresheners, candles, cablefillers, sealants, lubricating greases, strippable coatings, corrosionprotectors, etc. But oil gels have not been used as a base for thermalinterface materials. Exemplary embodiments of the present disclosure mayvary the type and quantities of the thermally reversible gels includedin a thermal interface material. By way of example, thermal interfacematerials disclosed herein may include a wide range of different typesand quantities of thermally reversible gels with a di-block and/ortri-block copolymer(s) (e.g., di-block styrenic copolymers, tri-blockstyrenic copolymers, etc.), oils and/or solvents blended with elastomers(e.g., thermoplastic elastomers, etc.), gelling agents, etc. One or moreof these above-listed materials may be selected for various exemplaryembodiments of the present disclosure and then varied to produceparticular gels (e.g., thermally reversible gelled fluids, oil gel andsolvent gel resin, etc.) with different characteristics for a giventhermal interface material.

For example, depending on the specific ingredients and formulation, aresulting oil gel may vary from a cohesive highly elastic continuousrubber network, to a weak gel, to a grease. Accordingly, thermalinterface materials of the present disclosure may include any of a widerange of thermally reversible gels, so as to be configured to provideone or more of thermally conductive gap fillers, thermally conductivegels, thermally conductive putties, thermally conductive dispensablematerials, and thermally conductive greases. In various exemplaryembodiments, the thermal interface material may have a hardness lessthan or equal to about 100 Shore A. Furthermore, some thermal interfacematerials based on oil gel may also be formulated to soften at a giventemperature (e.g., at 150 degrees Celsius, etc.), function as phasechange materials, etc.

In example embodiments of the present disclosure in which the thermalinterface material includes oil gel, the oil gel may comprise processoil and a gelling agent. Process oils are typically oils for which oneor more key properties are reported and controlled. Process oils and/orsolvents are typically used in manufacturing to modify the properties ofan article, improve the properties of an article, and/or impart desiredproperties to a finished article.

Example embodiments of thermal interface materials of the presentdisclosure may include naphthenic oils and solvents and/or paraffinicoils and solvents (e.g., isopars, etc.). Temperature stability of theoil and/or solvent is one example characteristic to be considered whenselecting the oil/solvent for a thermal interface material of thepresent disclosure. Because thermal interface materials may be exposedto varying, and relatively high, temperatures, in some embodiments ahigh temperature stable oil and/or solvent may be desirable.

Thermal interface materials according to the present disclosure may usethermoplastic materials (e.g., thermoplastic elastomers, etc.) for thegelling agent of the oil gel. Suitable thermoplastic materials includeblock copolymers, such as di-block and tri-block polymers (e.g.,di-block and tri-block styrenic polymers, etc.). Some exemplaryembodiments of a thermal interface material include block polymerscomprising polystyrene segments and rubber segments. With di-blockpolymers, a polystyrene segment is attached to a rubber segment, whiletri-block polymers include polystyrene segments on both ends of a rubbersegment. In oil gels made with tri-block styrenic polymers, the styrenesegments act as physical crosslinks with the rubber to form a highlyelastic continuous rubber network. Di-block polymers, however, do notform such physical crosslinks and an oil gel made with di-block polymerstends to resemble a grease rather than a solid rubber. Di-block andtri-block polymers may be used alone or together in various proportionsaccording to the desired characteristics for the thermal interfacematerial that will include the same. The rubber is the elastomericportion of such polymers and may be, for example, a saturated olefinrubber (such as polyethylene/butylene, polyethylene/propylene, etc.).

One or more thermally conductive fillers are added during processing tocreate a thermally conductive interface material in which one or morethermally conductive fillers will be suspended in, added to, mixed into,etc. the thermally reversible gel. For example, at least one thermallyconductive filler may be added to a mixture including gellable fluid andgelling agent before the gellable fluid and gelling agent have gelled orform the thermally reversible gel. As another example, at least onethermally conductive filler may be added to the gellable fluid and thengelling agent may be added to the mixture containing gellable fluid andthermally conductive filler. In yet another example, at least onethermally conductive filler may be added to the gelling agent and thengellable fluid may be added to the mixture containing gelling agent andthermally conductive filler. By way of further example, at least onethermally conductive filler may be added after the gellable fluid andgelling agent have gelled. For example, at least one thermallyconductive filler may be added to the gel when the gel may be cooled andbe loosely networked such that filler can be added. The amount ofthermally conductive filler in the thermally reversible gel may vary indifferent embodiments. By way of example, some exemplary embodiments ofa thermal interface material may include not less than 5 percent but notmore than 98 percent by weight of at least one thermally conductivefiller.

A wide range of different thermally conductive fillers may be used inexemplary embodiments of a thermal interface material according to thepresent disclosure. In some preferred embodiments, the thermallyconductive fillers have a thermal conductivity of at least 1 W/mK (Wattsper meter-Kelvin) or more, such as a copper filler having thermallyconductivity up to several hundred W/mK, etc. Suitable thermallyconductive fillers include, for example, zinc oxide, boron nitride,alumina, aluminum, graphite, ceramics, combinations thereof (e.g.,alumina and zinc oxide, etc.). In addition, exemplary embodiments of athermal interface material may also include different grades (e.g.,different sizes, different purities, different shapes, etc.) of the same(or different) thermally conductive fillers. For example, a thermalinterface material may include two different sizes of boron nitride. Byvarying the types and grades of thermally conductive fillers, the finalcharacteristics of the thermal interface material (e.g., thermalconductivity, cost, hardness, etc.) may be varied as desired.

Other suitable fillers and/or additives may also be added to a thermalinterface material to achieve various desired outcomes. Examples ofother fillers that may be added include pigments, plasticizers, processaids, flame retardants, extenders, electromagnetic interference (EMI) ormicrowave absorbers, electrically-conductive fillers, magneticparticles, etc. For example, tackifying agents, etc. may be added toincrease the tackiness of a thermal interface material, etc.

As another example, EMI or microwave absorbers, electrically-conductivefillers, and/or magnetic particles may be added such that the thermalinterface material may be operable or usable as an EMI and/or RFIshielding material. A wide range of materials may be added to a thermalinterface material according to exemplary embodiments, such as carbonyliron, iron silicide, iron particles, iron-chrome compounds, metallicsilver, carbonyl iron powder, SENDUST (an alloy containing 85% iron,9.5% silicon and 5.5% aluminum), permalloy (an alloy containing about20% iron and 80% nickel), ferrites, magnetic alloys, magnetic powders,magnetic flakes, magnetic particles, nickel-based alloys and powders,chrome alloys, and any combinations thereof. Other embodiments mayinclude one or more EMI absorbers formed from one or more of the abovematerials where the EMI absorbers comprise one or more of granules,spheroids, microspheres, ellipsoids, irregular spheroids, strands,flakes, powder, and/or a combination of any or all of these shapes.Accordingly, some exemplary embodiments may thus include thermalinterface materials that include or are based on thermally reversiblegels, where the thermal interface materials are also configured (e.g.,include or are loaded with EMI or microwave absorbers,electrically-conductive fillers, and/or magnetic particles, etc.) toprovide shielding.

By way of background, EMI absorbers convert electromagnetic energy intoanother form of energy through a process commonly referred to as a loss.Electrical loss mechanisms include conductivity losses, dielectriclosses, and magnetization losses. Conductivity losses refer to areduction in EMI resulting from the conversion of electromagnetic energyinto thermal energy. The electromagnetic energy induces currents thatflow within the EMI absorbers having a finite conductivity. The finiteconductivity results in a portion of the induced current generating heatthrough a resistance. Dielectric losses refer to a reduction in EMIresulting from the conversion of electromagnetic energy into mechanicaldisplacement of molecules within the EMI absorbers having a non-unitaryrelative dielectric constant. Magnetic losses refer to a reduction inEMI resulting from the conversion of electromagnetic energy into arealignment of magnetic moments within the EMI absorbers.

In some exemplary embodiments, a thermal interface material may includean adhesive layer. The adhesive layer may be a thermally conductiveadhesive to preserve the overall thermal conductivity. The adhesivelayer may be used to affix the thermal interface material to anelectronic component, heat sink, EMI shield, etc. The adhesive layer maybe formulated using a pressure-sensitive, thermally-conducting adhesive.The pressure-sensitive adhesive (PSA) may be generally based oncompounds including acrylic, silicone, rubber, and combinations thereof.The thermal conductivity is enhanced, for example, by the inclusion ofceramic powder.

In some exemplary embodiments, thermal interface materials includingthermally-reversible gel may be attached or affixed (e.g., adhesivelybonded, etc.) to one or more portions of an EMI shield, such as to asingle piece EMI shield and/or to a cover, lid, frame, or other portionof a multi-piece shield, to a discrete EMI shielding wall, etc.Alternative affixing methods can also be used such as, for example,mechanical fasteners. In some embodiments, a thermal interface materialthat includes thermally-reversible gel may be attached to a removablelid or cover of a multi-piece EMI shield. A thermal interface materialthat includes thermally-reversible gel may be placed, for example, onthe inner surface of the cover or lid such that the thermal interfacematerial will be compressively sandwiched between the EMI shield and anelectronic component over which the EMI shield is placed. Alternatively,a thermal interface material that includes thermally-reversible gel maybe placed, for example, on the outer surface of the cover or lid suchthat the EMI shield is compressively sandwiched between the EMI shieldand a heat sink. A thermal interface material that includesthermally-reversible gel may be placed on an entire surface of the coveror lid or on less than an entire surface. A thermal interface materialthat includes thermally-reversible gel may be applied at virtually anylocation at which it would be desirable to have an EMI absorber.

Aspects of the present disclosure will be further illustrated by thefollowing examples. The following examples are merely illustrative, anddo not limit this disclosure to the particular formulations in any way.

EXAMPLES Example 1

In this example, a thermal interface material (specifically athermally-conductive gap filler) including one or more aspects of thepresent disclosure was generally formed from di-block and tri-blockstyrenic copolymers, a paraffinic oil, and thermally conductive fillers.

In this example thermal interface material, the oil is about 14.1percent of the thermal interface material by weight, the di-blockstyrenic copolymer is about 4.2 percent of the thermal interfacematerial by weight, the tri-block styrenic copolymer is about 1.1percent of the thermal interface material by weight, and the thermallyconductive fillers are about 80.2 percent of the thermal interfacematerial by weight. The thermal interface material also includes anantioxidant that is about 0.1 percent of the thermal interface materialby weight and pigment that is about 0.4 percent of the thermal interfacematerial by weight.

The tri-block styrenic copolymer used in this example formulationincludes polyethylene/butylene as the elastomeric (or rubber) portion.The structure is predominantly tri-block and has a styrene to rubberratio of 29 to 71. The copolymer has a medium molecular weight and aglass transition temperature of −55° C.

The di-block styrenic copolymer used in this example formulationincludes polyethylene/propylene as the elastomeric (or rubber) portion.The structure is predominantly di-block and has a styrene to rubberratio of 37 to 63. The copolymer has a high molecular weight and a glasstransition temperature of −55° C.

For this example formulation, the thermally conductive filler includedtwo different grades of alumina. The first grade of alumina is groundaluminum oxide with mean particle size of 2 microns and is about 15.6percent of the thermal interface material by weight. The second grade ofalumina is a generally spherical aluminum oxide with a mean particlesize of 30 microns and is about 64.3 percent of the thermal interfacematerial by weight.

This example thermal interface material exhibited a thermal conductivityof 0.9 W/mK (as measured according to the Hot Disk method). The thermalinterface material exhibited a hardness of about 48 Shore 00 (threeseconds, as measured according to ASTM standard D2240-00).

An exemplary process will now be described, which may be used forpreparing a thermal interface material consistent with this Example 1.Alternative processes, however, may also be employed for making athermal interface material. In this example, the oil, the di-blockstyrenic copolymer, the tri-block styrenic copolymer, pigment andantioxidant may be mixed together to get a homogenized mixture. Themixture may then be heated to soften the polystyrene segments of thedi-block styrenic copolymer and the tri-block styrenic copolymer,freeing them to move with shear. The mixture may then be maintained atabout 150° C. for two to three hours with mixing until the mixtureachieves a smooth consistency. The thermally conductive fillers may thenbe added to the mixture, resulting in a mixture having the consistencyof wet sand. The mixture may then be cooled to a rubber consistency.Rather than immediately adding the thermally conductive fillers, thethermally conductive fillers may be added later. For example, thehomogenized mixture or resin may be cooled and stored before anythermally conductive fillers are added. After a time, the homogenizedmixture or resin may be re-heated and then the thermally conductivefillers may be added. After which, the mixture including the thermallyconductive fillers is cooled to a rubber consistency.

After the mixture with the thermally conductive fillers therein iscooled to a rubber consistency and while warm, the mixture may then beprocessed for use as a thermal interface material. In this Example 1,the warm mixture may be formed, etc. into sheets of material withrelease liners (e.g., for protection of the formed thermal interfacematerial during cutting, shipping, etc.) added to both sides of thesheets for final distribution. Alternatively, it should be appreciatedthat the warm mixture could be allowed to cool (by suitable coolingoperations) after the fillers are added, stored for later use, and thensubsequently re-warmed to be processed into thermal interface materials.The mixture may be formed into a thermal interface material sheet bycalendaring the mixture between two liner sheets. The nip (or gap)between a series of heated rollers may be set to the desired thicknessof the final thermal interface material. The mixture may then be runthrough the rollers to form a pad with a thickness as determined by thegap between the rollers. Simultaneously, liner sheets may be run throughthe rollers on either side of the mixture/thermal interface materialresulting in a finished thermal interface material that includes releaseliners on both sides of the thermal interface material. The releaseliners may be any suitable release liner, for example, Mylar liners.Alternatively, the release liner may only be located on one side of thethermal interface material, or there may be no release liner applied tothe thermal interface material.

In some other exemplary embodiments such as those in which thethermally-reversible gel is of very low hardness or grease-like at roomtemperature (or a cooled state), the gel might not have to be heated toadd the filler. Instead, the room-temperature or cool gel may be of lowenough viscosity that the gel does not need to be liquefied by heat toadd filler. The gel may be substantially liquid enough at roomtemperature or even in a cooled state to allow for the addition of oneor more fillers to the gel.

A thermal interface material may also be molded, such as by injectionmolding, instead of being calendared. Injection molding may permit threedimensionally shaped thermal interface materials to be created.

After the thermal interface material sheet has been calendared, it isready for use or further processing. The completed thermal interfacematerial sheet may be further processed in a manner similar to otherthermal interface materials. For example, the thermal interface materialsheet may be cut into smaller sheets, die-cut into specific shapes,laser cut, etc.

Thermal interface materials according to the present disclosure may bereused/reformed/recycled/etc. by reheating the material, which is unlikefor example, various known thermal interface materials that are notbased on thermally reversible gels. Accordingly, a thermal interfacematerial based on a thermally reversible gel may be reheated andreprocessed (e.g., reshaped, re-sized, etc.) in the manner describedabove.

Example 2

In this example, a thermal interface material including one or moreaspects of the present disclosure was generally formed from a di-blockstyrenic copolymer, a tri-block and di-block styrenic copolymer blend,paraffinic oil, and thermally conductive fillers.

In this example thermal interface material, the oil is about 13.5percent of the thermal interface material by weight, the di-blockstyrenic copolymer is about 1.7 percent of the thermal interfacematerial by weight, the di-block/tri-block copolymer blend is about 3.4percent of the thermal interface material by weight, and the thermallyconductive fillers are about 81 percent of the thermal interfacematerial by weight. The thermal interface material also includes anantioxidant that is about 0.1 percent of the thermal interface materialby weight and pigment that is about 0.3 percent of the thermal interfacematerial by weight.

The di-block styrenic copolymer used in this example formulationincludes polyethylene/propylene as the elastomeric (or rubber) portion.The structure is predominantly di-block and has a styrene to rubberratio of 37 to 63. The copolymer has a high molecular weight and a glasstransition temperature of −55° C.

The di-block/tri-block styrenic copolymer blend used in this exampleformulation includes polyethylene/butylene as the elastomeric (orrubber) portion. The blend is 30 percent tri-block and 70 percentdi-block and has a styrene to rubber ratio of 30 to 70. The copolymerblend has a low molecular weight and a glass transition temperature of−55° C.

For this example formulation, the thermally conductive filler includedtwo different thermally conductive fillers. The first thermallyconductive filler is a ground alumina tri-hydrate (ATH) with meanparticle size of 20 microns and is about 72.5 percent of the thermalinterface material by weight. The second thermally conductive filler isa fine zinc oxide (ZnO) with a mean particle size of 0.3 microns and isabout 8.5 percent of the thermal interface material by weight.

The thermal interface material of this example may be prepared andprocessed as described above in regard to Example 1.

This example thermal interface material exhibited a thermal conductivityof 1.53 W/mK (as measured according to the Hot Disk method). The thermalinterface material exhibited a hardness of about 75 Shore 00 (threeseconds, as measured according to ASTM standard D2240-00).

Example 3

In this example, a thermal interface material including one or moreaspects of the present disclosure was generally formed from a di-blockstyrenic copolymer, a tri-block styrenic copolymer, paraffinic oil, andboron nitride fillers.

In this example thermal interface material, the oil is about 43.2percent of the thermal interface material by weight, the di-blockstyrenic copolymer is about 2.9 percent of the thermal interfacematerial by weight, the tri-block copolymer is about 6.7 percent of thethermal interface material by weight, and the thermally conductivefiller is about 46.1 percent of the thermal interface material byweight. The thermal interface material also includes an antioxidant thatis about 0.2 percent of the thermal interface material by weight andpigment that is about 1 percent of the thermal interface material byweight.

The tri-block styrenic copolymer used in this example formulationincludes polyethylene/butylene as the elastomeric (or rubber) portion.The structure is predominantly tri-block and has a styrene to rubberratio of 29 to 71. The copolymer has a medium molecular weight and aglass transition temperature of −55° C.

The di-block styrenic copolymer used in this example formulationincludes polyethylene/propylene as the elastomeric (or rubber) portion.The structure is predominantly di-block and has a styrene to rubberratio of 37 to 63. The copolymer has a high molecular weight and a glasstransition temperature of −55° C.

For this example formulation, the thermally conductive filler includedboron nitride with a mean particle size of 125 microns.

The thermal interface material of this example may be prepared andprocessed as described above in Example 1.

This example thermal interface material exhibited a thermal conductivityof 2.7 W/mK (as measured according to the Hot Disk method). The thermalinterface material exhibited a hardness of about 80 Shore 00 (threeseconds, as measured according to ASTM standard D2240-00).

Example 4

In this example, a thermal interface material (specifically thermalgrease) including one or more aspects of the present disclosure wasgenerally formed from a di-block styrenic copolymer, paraffinic oil, anda boron nitride filler.

In this example thermal interface material, the oil is about 51.3percent of the thermal grease by weight, the di-block styrenic copolymeris about 33.3 percent of the thermal grease by weight, and the thermallyconductive filler is about 15.4 percent of the thermal grease by weight.

The di-block styrenic copolymer used in this example formulationincludes polyethylene/propylene as the elastomeric (or rubber) portion.The structure is predominantly di-block and has a styrene to rubberratio of 37 to 63. The copolymer has a high molecular weight and a glasstransition temperature of −55° C.

For this example formulation, the thermally conductive filler includedboron nitride with a mean particle size of 210 microns.

This example thermal grease exhibited a thermal conductivity of 0.8 W/mK(as measured according to the Hot Disk method). As this example thermalinterface material is a grease, it has no measureable hardness.

Example 5

In this example, a thermal interface material including one or moreaspects of the present disclosure was generally formed from a di-blockstyrenic copolymer, a tri-block styrenic copolymer, paraffinic oil, anda boron nitride filler.

In this example thermal interface material, the oil is about 42.4percent of the thermal interface material by weight, the di-blockstyrenic copolymer is about 2.8 percent of the thermal interfacematerial by weight, the tri-block copolymer is about 6.6 percent of thethermal interface material by weight, and the thermally conductivefiller is about 47.1 percent of the thermal interface material byweight. The thermal interface material also includes an antioxidant thatis about 0.2 percent of the thermal interface material by weight andpigment that is about 0.9 percent of the thermal interface material byweight.

The tri-block styrenic copolymer used in this example formulationincludes polyethylene/butylene as the elastomeric (or rubber) portion.The structure is predominantly tri-block and has a styrene to rubberratio of 29 to 71. The copolymer has a medium molecular weight and aglass transition temperature of −55° C.

The di-block styrenic copolymer used in this example formulationincludes polyethylene/propylene as the elastomeric (or rubber) portion.The structure is predominantly di-block and has a styrene to rubberratio of 37 to 63. The copolymer has a high molecular weight and a glasstransition temperature of −55° C.

For this example formulation, the thermally conductive filler includedboron nitride with a mean particle size of 125 microns.

The thermal interface material of this example may be prepared andprocessed as described above in Example 1.

This example thermal interface material exhibited a thermal conductivityof 3.37 W/mK (as measured according to the Hot Disk method). The thermalinterface material exhibited a hardness of about 88 Shore 00 (threeseconds, as measured according to ASTM standard D2240-00).

Example 6

In this example, a thermal interface material including one or moreaspects of the present disclosure was generally formed from a di-blockstyrenic copolymer, a tri-block/di-block styrenic copolymer blend,paraffinic oil, and thermally conductive fillers.

In this example thermal interface material, the oil is about 42.5percent of the thermal interface material by weight, the di-blockstyrenic copolymer is about 5.3 percent of the thermal interfacematerial by weight, the di-block/tri-block copolymer blend is about 10.6percent of the thermal interface material by weight, and the thermallyconductive fillers are about 40.3 percent of the thermal interfacematerial by weight. The thermal interface material also includes anantioxidant that is about 0.2 percent of the thermal interface materialby weight and pigment that is about 1.1 percent of the thermal interfacematerial by weight.

The di-block styrenic copolymer used in this example formulationincludes polyethylene/propylene as the elastomeric (or rubber) portion.The structure is predominantly di-block and has a styrene to rubberratio of 37 to 63. The copolymer has a high molecular weight and a glasstransition temperature of −55° C.

The di-block/tri-block styrenic copolymer blend used in this exampleformulation includes polyethylene/butylene as the elastomeric (orrubber) portion. The blend is 30 percent tri-block and 70 percentdi-block and has a styrene to rubber ratio of 30 to 70. The copolymerblend has a low molecular weight and a glass transition temperature of−55° C.

For this example formulation, the thermally conductive fillers includetwo different thermally conductive fillers. The first thermallyconductive filler is aluminum (Al) with a mean particle size of 5microns and is about 27.6 percent of the thermal interface material byweight. The second thermally conductive filler is zinc oxide (ZnO) witha mean particle size of 0.3 microns and is about 12.7 percent of thethermal interface material by weight.

The thermal interface material of this example may be prepared andprocessed as described above in Example 1.

This example thermal interface material exhibited a thermal conductivityof 0.3 W/mK (as measured according to the Hot Disk method). The thermalinterface material exhibited a hardness of about 28 Shore 00 (threeseconds, as measured according to ASTM standard D2240-00).

In exemplary embodiments, a material (e.g., a thermal interfacematerial, an electrically-conductive thermal insulator, an EMI absorbingthermal insulator, etc.) includes at least one filler (e.g., athermally-conductive filler, an electrically-conductive filler, anelectromagnetic interference (EMI) absorber, etc.) in a thermallyreversible gel including di-block and tri-block styrenic copolymers andprocess oil. A ratio of the process oil to the di-block and tri-blockstyrenic copolymers may be within a range from 4 to 1 (4:1) to 12 to 1(12:1). Stated differently, the ratio of the process oil to the di-blockand tri-block styrenic copolymers is at least 4 to 1 but not more than12 to 1. For example, the ratio of process oil to the di-block andtri-block styrenic copolymers may be about 4:1, 4.3:1, 4.4:1, 4.5:1,4.6:1, 11:1, 11.1:1, 12:1, or other ratio between 4:1 to 12:1. In someexemplary embodiments, the ratio of the process oil to the di-block andtri-block styrenic copolymers may be at least 4:1 but not more than 5:1or at least 11:1 but not more 12:1.

In some exemplary embodiments, the at least one filler comprises anelectrically-conductive filler. And, the material comprises anelectrically-conductive thermal insulator.

In some exemplary embodiments, the at least one filler comprises anelectromagnetic interference (EMI) absorber. And, the material comprisesan EMI absorbing thermal insulator.

In some exemplary embodiments, the at least one filler comprises athermally-conductive filler. And, the material comprises a thermalinterface material.

In some exemplary embodiments, the at least one filler comprises anelectrically-conductive filler, an electromagnetic interference (EMI)absorber, and/or a thermally-conductive filler. For example, the fillermay comprise an electrically-conductive filler, an electromagneticinterference (EMI) absorber, and a thermally-conductive filler.Alternatively, the filler may comprise only one anelectrically-conductive filler, an electromagnetic interference (EMI)absorber, or a thermally-conductive filler. As yet another example, thefiller may comprise any combination of an electrically-conductivefiller, an electromagnetic interference (EMI) absorber, and/or athermally-conductive filler.

The ratio of di-block styrenic copolymer to tri-block styrenic copolymermay be at least about 0.85 to 1 (0.85:1) but not more than 1.6 to 1(1.6:1). For example, the ratio of di-block styrenic copolymer totri-block styrenic copolymer may be about 0.85:1, 1:1, 1.2:1, 1:5.1,1.6:1, or other ratio between 0.85:1 and 1.6:1. In some exemplaryembodiments, the ratio of di-block styrenic copolymer to tri-blockstyrenic copolymer may be at least 1:1 but not more than 1.6:1.

The material may include at least one or more fillers and/or additives(e.g., an electrically-conductive filler, an electromagneticinterference (EMI) absorber, a thermally-conductive filler, etc.) in atotal amount less than or equal to about 99 percent of the material byweight. For example, the material may include at least one or morefillers and/or additives in a total amount that is about 40 percent toabout 99 percent of the material by weight (e.g., 47%, 48%, 94%, 95%,96% by weight, etc.).

The material may have a hardness less than or equal to about 90 Shore 00(three seconds, as measured according to ASTM standard D2240-00). Forexample, the material may have a hardness within a range from about 60to about 90 Shore 00 (three seconds, as measured according to ASTMstandard D2240-00), such as a hardness of 72, 80, 81, 85, etc.

In an exemplary embodiment, the ratio of the process oil to the di-blockand tri-block styrenic copolymers may be about 4.5 to 1. The ratio ofthe di-block styrenic copolymer to the tri-block styrenic copolymer maybe about 1.5 to 1. The material (e.g., a thermal interface material, anelectrically-conductive thermal insulator, an EMI absorbing thermalinsulator, etc.) may include at least one or more fillers and/oradditives (e.g., a thermally-conductive filler, anelectrically-conductive filler, an EMI absorber, etc.) in a total amountof about 94 or 95 percent of the material by weight. The material mayhave a hardness of about 85 Shore 00 (three seconds, as measuredaccording to ASTM standard D2240-00).

In another exemplary embodiment, the ratio of the process oil to thedi-block and tri-block styrenic copolymers may be about 11 or 11.1 to 1.The ratio of the di-block styrenic copolymer to the tri-block styreniccopolymer may be about 1.5 or 1.6 to 1. The material (e.g., a thermalinterface material, an electrically-conductive thermal insulator, an EMIabsorbing thermal insulator, etc.) may include at least one or morefillers and/or additives (e.g., a thermally-conductive filler, anelectrically-conductive filler, an EMI absorber, etc.) in a total amountof about 94 or 95 percent of the material by weight. The material mayhave a hardness of about 72 Shore 00 (three seconds, as measuredaccording to ASTM standard D2240-00).

In a further exemplary embodiment, the ratio of the process oil to thedi-block and tri-block styrenic copolymers may be about 4.5 to 1. Theratio of the di-block styrenic copolymer to the tri-block styreniccopolymer may be about 1.2 to 1. The material (e.g., a thermal interfacematerial, an electrically-conductive thermal insulator, an EMI absorbingthermal insulator, etc.) may include at least one or more fillers and/oradditives (e.g., a thermally-conductive filler, anelectrically-conductive filler, an EMI absorber, etc.) in a total amountof about 47 or 48 percent of the material by weight. The material mayhave a hardness of about 80 Shore 00 (three seconds, as measuredaccording to ASTM standard D2240-00).

In yet another exemplary embodiment, the ratio of the process oil to thedi-block and tri-block styrenic copolymers may be about 4.3 or 4.4 to 1.The ratio of the di-block styrenic copolymer to the tri-block styreniccopolymer may be about 1 to 1. The material (e.g., a thermal interfacematerial, an electrically-conductive thermal insulator, an EMI absorbingthermal insulator, etc.) may include at least one or more fillers and/oradditives (e.g., a thermally-conductive filler, anelectrically-conductive filler, an EMI absorber, etc.) in a total amountof about 95 or 96 percent of the material by weight. The material mayhave a hardness of about 81 Shore 00 (three seconds, as measuredaccording to ASTM standard D2240-00).

In exemplary embodiments, a material (e.g., a thermal interfacematerial, an electrically-conductive thermal insulator, an EMI absorbingthermal insulator, etc.) includes at least one filler (e.g., athermally-conductive filler, an electrically-conductive filler, an EMIabsorber, etc.) in a thermally reversible gel including di-block andtri-block styrenic copolymers and process oil. The material may have ahardness less than or equal to about 88 Shore 00 (three seconds, asmeasured according to ASTM standard D2240-00). The process oil may beless than or equal to about 43.2 percent of the material by weight. Thedi-block styrenic copolymer may be less than or equal to about 5.3percent of the material by weight. The material may further include atleast one filler that is less than or equal to about 98 percent of thematerial by weight. The material may also include a di-block andtri-block styrenic copolymer blend that is less than or equal to about10.6 percent of the material by weight. Or, the material may includetri-block styrenic copolymer that is less than or equal to about 6.7percent of the material by weight.

In an exemplary embodiment, the material has a hardness within a rangefrom 28 Shore 00 to 88 Shore 00 (three seconds, as measured according toASTM standard D2240-00). The process oil (e.g., paraffinic oil, etc.) isabout 13.5 percent to about 43.2 percent of the material by weight. Thedi-block styrenic copolymer is about 1.7 percent to about 5.3 percent ofthe material by weight. The at least one filler is about 40.3 percent toabout 81 percent of the material by weight. The material also includesthe di-block and tri-block styrenic copolymer blend that is about 3.4percent to about 10.6 percent of the material by weight, or thetri-block styrenic copolymer that is about 1.1 percent to about 6.7percent of the material by weight.

In some exemplary embodiments, the material may comprise athermally-conductive gap filler that is soft at room temperature andthat is operable for allowing heat generated by an operating electricalcomponent to pass through the gap filler. The material may be free ofsilicone. The material may be compliant, soft at room temperature, andoperable for filling a gap between thermal transfer surfaces to therebyallow heat generated by an operating electrical component to pass fromone of the thermal transfer surfaces through the material to the otherone of the thermal transfer surfaces. The material may be formulated tosoften at a temperature of about 150 degrees Celsius. The at least onefiller may comprise one or more of boron nitride, alumina, aluminum,graphite, copper, and combinations thereof. The material may include notless than 5 percent but not more than 98 percent by weight of the atleast one thermally conductive filler.

The above described example formulations illustrate the variability andadaptability of materials based on thermally reversible gels. Theexample formulations described above illustrate that those examplematerials exhibit a wide range of characteristics. For example, thehardness of the final material may range from a grease (Example 4) to ahardness of 88 shore 00 (Example 5). The thermal conductivity may rangefrom 0.3 W/mK (Example 6) to 3.37 W/mK (Example 5) in exemplaryembodiments in which the material comprises a thermal interfacematerial. It can be seen that by varying the type and percentages of theoil, gelling agent, and/or fillers, various materials having differentcharacteristics (e.g., higher or lower thermal conductivities, higher orlower hardness ratings, etc.) may be created. It should be appreciatedthat numerical values and particular formulations are provided in theseexamples, and in this disclosure, for illustrative purposes only. Theparticular values and formulations provided are not intended to limitthe scope of the present disclosure.

Example embodiments are provided so that this disclosure will bethorough, and will fully convey the scope to those who are skilled inthe art. Numerous specific details are set forth such as examples ofspecific components, devices, and methods, to provide a thoroughunderstanding of embodiments of the present disclosure. It will beapparent to those skilled in the art that specific details need not beemployed, that example embodiments may be embodied in many differentforms and that neither should be construed to limit the scope of thedisclosure. In some example embodiments, well-known processes,well-known device structures, and well-known technologies are notdescribed in detail.

The terminology used herein is for the purpose of describing particularexample embodiments only and is not intended to be limiting. As usedherein, the term “and/or” includes any and all combinations of one ormore of the associated listed items. Also as used herein, the singularforms “a”, “an” and “the” may be intended to include the plural forms aswell, unless the context clearly indicates otherwise. The terms“comprises,” “comprising,” “including,” and “having,” are inclusive andtherefore specify the presence of stated features, integers, steps,operations, elements, and/or components, but do not preclude thepresence or addition of one or more other features, integers, steps,operations, elements, components, and/or groups thereof. The methodsteps, processes, and operations described herein are not to beconstrued as necessarily requiring their performance in the particularorder discussed or illustrated, unless specifically identified as anorder of performance. It is also to be understood that additional oralternative steps may be employed.

When an element or layer is referred to as being “on”, “engaged to”,“connected to” or “coupled to” another element or layer, it may bedirectly on, engaged, connected or coupled to the other element orlayer, or intervening elements or layers may be present. In contrast,when an element is referred to as being “directly on,” “directly engagedto”, “directly connected to” or “directly coupled to” another element orlayer, there may be no intervening elements or layers present. Otherwords used to describe the relationship between elements should beinterpreted in a like fashion (e.g., “between” versus “directlybetween,” “adjacent” versus “directly adjacent,” etc.). As used herein,the term “and/or” includes any and all combinations of one or more ofthe associated listed items.

Although the terms first, second, third, etc. may be used herein todescribe various elements, components, regions, layers and/or sections,these elements, components, regions, layers and/or sections should notbe limited by these terms. These terms may be only used to distinguishone element, component, region, layer or section from another region,layer or section. Terms such as “first,” “second,” and other numericalterms, “next,” etc., when used herein, do not imply a sequence or orderunless clearly indicated by the context. Thus, a first element,component, region, layer or section discussed below could be termed asecond element, component, region, layer or section without departingfrom the teachings of the example embodiments.

Spatially relative terms, such as “inner,” “outer,” “beneath”, “below”,“lower”, “above”, “upper” and the like, may be used herein for ease ofdescription to describe one element or feature's relationship to anotherelement(s) or feature(s) as illustrated in the figures. Spatiallyrelative terms may be intended to encompass different orientations ofthe device in use or operation in addition to the orientation depictedin the figures. For example, if the device in the figures is turnedover, elements described as “below” or “beneath” other elements orfeatures would then be oriented “above” the other elements or features.Thus, the example term “below” can encompass both an orientation ofabove and below. The device may be otherwise oriented (rotated 90degrees or at other orientations) and the spatially relative descriptorsused herein interpreted accordingly.

The disclosure herein of particular values and particular ranges ofvalues for given parameters are not exclusive of other values and rangesof values that may be useful in one or more of the examples disclosedherein. Moreover, it is envisioned that any two particular values for aspecific parameter stated herein may define the endpoints of a range ofvalues that may be suitable for the given parameter (i.e., thedisclosure of a first value and a second value for a given parameter canbe interpreted as disclosing that any value between the first and secondvalues could also be employed for the given parameter). Similarly, it isenvisioned that disclosure of two or more ranges of values for aparameter (whether such ranges are nested, overlapping or distinct)subsume all possible combination of ranges for the value that might beclaimed using endpoints of the disclosed ranges.

The foregoing description of the embodiments has been provided forpurposes of illustration and description. It is not intended to beexhaustive or to limit the invention. Individual elements or features ofa particular embodiment are generally not limited to that particularembodiment, but, where applicable, are interchangeable and can be usedin a selected embodiment, even if not specifically shown or described.The same may also be varied in many ways. Such variations are not to beregarded as a departure from the invention, and all such modificationsare intended to be included within the scope of the invention.

What is claimed is:
 1. A material comprising at least one filler in athermally reversible gel including block copolymer and process oil,wherein the material comprises a pad formulated to be compliant againsta surface of a device at room temperature and during operation of thedevice.
 2. The material of claim 1, wherein the block copolymercomprises di-block copolymer.
 3. The material of claim 1, wherein theblock copolymer comprises di-block styrenic copolymer.
 4. The materialof claim 1, wherein the block copolymer comprises di-block and tri-blockcopolymers.
 5. The material of claim 1, wherein the block copolymercomprises di-block and tri-block styrenic copolymers.
 6. The material ofclaim 1, wherein the block copolymer comprises di-block copolymer ortri-block copolymer.
 7. The material of claim 1, wherein the blockcopolymer comprises tri-block copolymer.
 8. The material of claim 1,wherein the block copolymer comprises tri-block styrenic copolymer. 9.The material of claim 1, wherein the block copolymer comprises styreniccopolymer.
 10. The material of claim 1, wherein a ratio of the processoil to the block copolymer is at least about 4 to 1 but not more thanabout 12 to
 1. 11. The material of claim 1, wherein a ratio of theprocess oil to the block copolymer is not more than about 5 to
 1. 12.The material of claim 1, wherein a ratio of the process oil to the blockcopolymer is at least about 11 to
 1. 13. The material of claim 1,wherein a ratio of the process oil to the block copolymer is about 4.5to
 1. 14. The material of claim 1, wherein: the material includes the atleast one filler in a total amount that is about 40 percent to about 99percent of the material by weight; and/or the material has a hardnessthat is at least about 60 Shore 00 but not more than 90 Shore 00; and/orthe material is silicone free, such that the material is usable with nooccurrence of silicone migration or volatility due to the absence ofsilicone in the formulation; and/or the process oil is less than orequal to about 43.2 percent of the material by weight.
 15. The materialof claim 1, wherein the at least one filler comprises anelectrically-conductive filler.
 16. The material of claim 15, whereinthe material comprises an electrically-conductive thermal insulator. 17.The material of claim 1, wherein the at least one filler comprises anelectromagnetic interference (EMI) absorber.
 18. The material of claim17, wherein the material comprises an EMI absorbing thermal insulator.19. The material of claim 1, wherein the at least one filler comprises athermally-conductive filler.
 20. The material of claim 19, wherein thematerial comprises a thermal interface material.
 21. The material ofclaim 1, wherein the at least one filler comprises anelectrically-conductive filler, an electromagnetic interference (EMI)absorber, and/or a thermally-conductive filler.
 22. The material ofclaim 1, wherein the device includes an electrical component, andwherein the pad is formulated to be compliant against a surface of theelectrical component at room temperature and during operation of theelectrical component.